O-alkyl-o-{8 7-substituted-benzisoxazol(3)yl{9 -(thiono)-phosphoric (phosphonic) acid esters

ABSTRACT

O-alkyl-O-(7-substituted-benzisoxazol(3)yl)-(thiono)-phosphoric (phosphonic) acid esters of the general formula   in which X is oxygen or sulfur, R is alkyl of 1 to 6 carbon atoms, and R1 is alkyl or alkoxy of 1 to 6 carbon atoms, and Y is alkoxy of 1 to 6 carbon atoms or halogen, WHICH POSSESS INSECTICIDAL, ACARICIDAL, NEMATICIDAL AND FUNGICIDAL PROPERTIES.

United States Patent 11 1 Lorenz et al.

1 Oct. 21, 1975 l l O-ALKYL-O-[7-SUBSTITUTED- BENZISOXAZOL(3)YL]-(THIONO)- PHOSPHORIC (PHOSPHONIC) ACID ESTERS [75] Inventors: Walter Lorenz, Wuppertal; Ingeborg Hammann; Wolfgang Behrenz, both of Cologne; Wilhelm Stendel, Wuppertal, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Apr. 24, 1973 [21] Appl. No: 354,032

[30] Foreign Application Priority Data Primary Examiner Raymond V. Rush Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT O-alkyl-O-[7-substituted-benzisoxazol( 3 )yl I-(thiono phosphoric (phosphonic) acid esters of the general formula (I) /OR in which X is oxygen or sulfur,

R is alkyl of 1 to 6 carbon atoms, and

R is alkyl or alkoxy of i to 6 carbon atoms, and

Y is alkoxy of 1 to 6 carbon atoms or halogen, which possess insecticidal, acaricidal, nematicidal and fungicidal properties.

4 Claims, N0 Drawings O-ALKYL-O-[7-SUBSTITUTED- BENZISOXAZOL( 3 )YLl-(THIONO )-PHOSPHORIC (PHOSPHONIC) ACID ESTERS The present invention relates to and has for its objects the provision of particular new O-alkyl--[7- substituted-benzisoxazol( 3 )yl]-(thiono )-phosphoric (phosphonic) acid esters, i.e., 0,0-dialkyl-0-[7-alkoxybenzisoxazol(3yl]phosphoric acid esters, their 7-halo counterparts and their thiono and/or alkanephosphonic acid ester analogues which possess insecticidal, acaricidal, nematicidal and fungicidal properties, active compositions in the form of mixtures of such com pounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids, nematodes and fungi with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification DAS 1,253,7l3 and German Published Specification DOS 2,040,410 that chlorine'substituted and/or methyl-substituted benzisoxazolo (thiono)phosphoric and phosphonic acid esters, for example 0,0-dimethyl (Compound A) or 0,0-diethyl-O-[-chlorobenzisoxazol (3)yl]-thionophosphoric acid ester (Compound 8) or O-ethyl'O-[Schloro- (Compound C) or 7-methylbenzisoxazol( 3 )yl]-thionoethanephosphonic acid ester (Compound D), exhibit insecticidal activity.

The present invention provides, as new compounds, the benzisoxazolo( thio no )phosphoric phosphonic) acid esters of the general formula in which X is oxygen or sulfur,

R is alkyl of l to 6 carbon atoms, and

R is alkyl or alkoxy of 1 to 6 carbon atoms, and

Y is alkoxy of l to 6 carbon atoms or halogen.

Preferably, R is straight or branched lower alkyl of l to 4 carbon atoms, R is lower alkoxy or alkyl or 1 to 4 carbon atoms, and Y is chlorine, bromine, iodine or lower alkoxy such as methoxy, ethoxy or isopropoxy.

Surprisingly, the benzisoxazolo(thiono )phosphoric(- phosphonic) acid esters according to the invention display a substantially better insecticidal, especially soilinsecticidal, and acaricidal action in part accompanied by a nematicidal and fungicidal action, than the known chlorine-substituted and/or methyl-substituted benzisoxazolo(thiono)phosphoric acid esters of analogous structure and identical type of action. Furthermore, the products according to the present invention may also be employed successfully in the veterinary medicine field, against such animal pests (ectoparasites) as parasitic fly larvae. The compounds according to the invention thus represent a genuine enrichment of the art.

Furthermore, the new compounds contribute to satisfying the great demand for new active compounds in the field of pesticides. This demand results from the fact that the commercially available agents have to meet constantly higher standards, particularly in respect of questions of protection of the environment, such as low toxicity to warm-blooded animals, low phytotoxicity, rapid degradation in and on the plant with short minimum intervals to be observed between spraying with pesticide and harvesting, and activity against resistant pests. Thus, for example, over the course of the years blowfly larvae have, in various areas, become resistant towards the phosphoric acid esters and carbamates hitherto employed, so that the success in combating them is dubious in many areas. To ensure economical animal raising in the areas subject to attack, there is therefore a demand for agents by means of which, for example, blowfly larvae of resistant strains, such as of the genus Lucilia, can be combated reliably. For example, the Goondiwindi strain of Lucilia cuprina has become highly resistant towards the compounds hitherto used, However, the active compounds according to the invention act both against the normally sensitive strains and against the resistant strains of blowfly larvae.

Preferably, R is straight or branched alkyl with l to 4 carbon atoms, R is alkoxy or alkyl with, in either case, 1 to 4 carbon atoms, and Y is chlorine, bromine, iodine, methoxy, ethoxy or isopropoxy.

The present invention also provides a process for the preparation of a benzisoxazolo(thiono)phosphoric(- phosphonic) acid ester of the formula (I) in which a 3- hydroxy-benzisoxazole of the general formula is reacted, in the presence of an acid-acceptor or in the form of an alkali metal, alkaline earth metal or ammonium salt thereof, with a (thiono)phosphoric(phosphonic) acid ester halide of the general formula Hal (Ill),

CH O 3" (llla) (llu) -Continued OCH acid binding agent N (lV) HCl (C2H5O) P O The following may be mentioned as examples of the benzisoxazole derivatives (II) and (thiono)phosphoric (phosphonic) acid ester halides (III) which can be used as starting materials: 7-chloro-, -bromo-, -iodo-, -methoxy-, -ethoxyor -isopropoxy-3hydroxybenzisoxazole, as well as 0,0-dimethyl-, 0,0-diethyl-, 0,0-dipropyl-, 0,0-di-isopropyl-, -methyl-O-ethyl-, O-methyl-O-isopropyl-, O-ethyl-O-isopropyl, O-methyl-O- butyl-, 0,0-dibutyl-, 0,0-di-isobutylor O-tert.-butyl-O- methyl-phosphoric acid ester chloride and the corresponding thiono analogues, as well as O- methylmethane-, 0-ethyl-propane-, O-isopropyl-ethane- O-butyl-methane-, O-methyl-isopropane-, O-methylethane-, O-ethyl-ethane-, O-propyl-methaneor O-butylethane-phosphonic acid ester chloride and the corresponding thiono compounds.

The (thiono)phosphoric(phosphonic) acid esters required as starting materials are known and can be prepared according to customary processes, as can the 3- hydroxy-benzisoxazoles in question (see Chem. Ber. 100, 954 960 (1967)).

The preparative process is preferably carried out with the use of a suitable solvent or diluent. As such it is possible to use practically all inert organic solvents, especially aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene,

-benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, ethers, for example diethyl ether, dibutyl ether and dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as acetonitrile and propionitrile.

All customary acid-binding agents can be used as acid-acceptors. Alkali metal carbonates and alcoholates, such as sodium or potassium carbonate, sodium or potassium methylate and sodium or potassium ethylate, have proved particularly successful, as have aliphatic, aromatic and heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied over a fairly wide range. In general, it is about 0 to 120C, preferably about 40 to 70C. The reaction is generally carried out under normal pressure.

To carry out the process, the starting compounds are in most cases employed in equimolar amounts. An excess of one or other reactant produces no substantial advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents and in the presence of an acid acceptor, at the indicated temperatures, and after stirring for several hours if appropriate while warming the reaction mixture is worked up in the usual manner.

The compounds according -to the invention are in most cases obtained in the form of colorless or colored oils which cannot be distilled without decomposition but can be freed of the last volatile constituents by socalled slight distillation, that is to say prolonged heating under reduced pressure to moderately elevated temperatures, and can be purified in this way. They are characterized, above all, by refractive indexes. Some of the compounds are obtained in a crystalline form having a sharp melting point.

As has already been mentioned, the new benzisoxazolo(thiono)phosphoric(phosphonic) acid esters are distinguished by an outstanding insecticidal and acaricidal activity against plant pests, pests harmful to health and pests of stored products. Herein, they possess aa good action against both sucking and biting insects and against mites (Acarina). Furthermore, the products may be employed successfully in the veterinary medicine field against animal pests (ectoparasites) such as parasitic fly. larvae. At the same time they display a low phytotoxicity and in part also display nematicidal, soil-insecticidal and fungicidal properties.

For these reasons, the compounds according to the invention serve as pesticides in plant protection and the protection of stored products, and also in the hygiene and veterinary fields.

To the sucking insects there belong, in the main, aphids (Aphididae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosip/zum pisi) and the potato aphid (Mac-rosiphum solamfolii), the Currant gall aphid (Cryptomyzus korschelti), the rosy apply aphid (Sappap/zis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry blackfly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspz'diotus hederae) and the soft scale (Lecam'um hes peridum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Herc-inothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex Iectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Trialoma infestans) and, further, cicadas, such as Euscelis bilobams and Nephotettix bipunctatus.

In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipenm's) the gypsy moth (Lymantria dispar), the browntail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segeturn), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kulmiella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera), for example the granary weevil (Sirophilus granarius Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cqchleariae), the blossom beetle (MeIigeI/zes aeneus), the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius Acanthoscelides obtectus), the leatherbeetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium custaneum), the northern corn billbug (Calandra or Siraphilus zeumais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitar) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (melolonlha melolontlza); cockroaches, such as the German cockroach(Blattella germanica), American cockraoch (Periplaneta americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus), and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Cal- Iiphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stepliensi).

With the mites (Acarina) there are classed, in particular, the spider mites (tetrahychidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (paraletranychus pilosus Panonychus ulmi), gall mites, for example the blackcurrant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata).

When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the present compounds are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed-substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffms (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, nematicides and fungicides, or bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-l0%, preferably 0.0ll%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.000l-%, and preferably 0.0l95% by weight of the mixture.

The active compounds can also be ,used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely'divided form, e.g.- average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, eg about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids, nematodes and fungi, and more particularly methods of combating at least one of insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (c) such nematodes, (d) such fungi, and (e) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally, nematicidally or fungicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrustation, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 Drosophila test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifer, and the concentrate is diluted with water to the desired concentration.

1 cm of the preparation of the active compound is applied with a pipette to a filter paper disc of 7 cm diameter. The wet disc is placed in a glass vessel containing 50 vinegar flies (Drosophila melanogaster) and covered with a glass plate.

After the specified periods of time, the destruction is determined as a percentage: 100% means that all the flies are killed; means that none of the flies are killed.

The active compounds, their concentrations, the evaluation times and the degree of destruction can be seen from the following Table l:

Table 1 (Drosophila test) Active compound Active com- Degree of pound condestructcentration ion in 7:

in A by after I weight day C H 10 3 0.1 100 0 0.01 90 0.0Ul U I N I S 2 s)2 (known) (E) 0 1 100 0 Ol C I N S 0 001 0 20 u o 'z rJ-z (known) 0 0.1 lOO 0.01 100 s 0.001 75 OCH 3O 0 I00 .l P 0.0] lOO N Is| 0.001 100 3 o --P(OC- H OC H i 0 l 100 N 0 01 I00 I S 0 0O] 95 u Q (OCH;,1-

I 0.1 100 N 0.01 100 5 0.001 100 0.0001 100 0 ---P(OCH ,1 0.00001 40 l Q 0.! I00 I 0.0l I00 I N 0.001 100 S I O (OCt-H l-l (2) Cl 0 l lOO 0:01 100 N 0.001 100 Table l-Continued (Drosophilu test) Table 2 (Phaedon larvae test) Active compound Active com- Degree of Active compound Active com- Degree of pound condestruct- 5 pound con destruccentrution ion in centrution tion in "/1 in by after 1 in by after 3 s y weight days Br I I 0 1 100 0.1 100 [0 C l N 0101 100 N 0.01 100 0.001 0 0.001 100 fi s 0.0001 so P( H3)-. O (known) (A) (8) -P(OCH3)2 N 0.1 100 Cl 0.01 100 0.001 0 o -P oC2 5)2 (known) (B) N 0.1 100 0.01 100 OCH o 1 (oc11=, 0 0.1 100 (10 I 0.01 100 O 0.1 100 a l 0.01 100 N 0.001 75 o 0.1 100 0 -1 5 0.01 100 1 1 l N 0.001 95 I S -home I OC;,H;-i

O 0 1 100 l 0 01 100 O 0.1 100 N 0 001 65 40 I 0.01 100 a I N 0.001 60 o P c n E ocz Qh EXAMPLE 2 o 0.1 100 l 0.0] 100 Phaedon larvae test N 0901 85 I Solvent: 3 parts by weight of acetone fi Emulsifier: 1 part by weight of alkylaryl polyglycol (2) 0 s ether To produce a suitable preparation of active comcl pound, 1 part by weight of the active compound is mixed with the stated amount of solvent which contains Q 1 d h l 0.1 100 the stated amount of emu s1 ier an t e concentrate is N 0 01 100 diluted with water to the desired concentration. I f 0.001 100 Cabbage leaves (Brassica oleracea) are sprayed with O i the preparat on of the actlve compound until dripping \ocms wet and are infested with mustard beetle larvae (Pliae- (5) don cochleariae).

After the specified periods of time, the degree of destruction is determined as a percentage. Here, 100% EXAMPLE 3 means that all of the beetle larvae have been killed; 0% D l means that no beetle larvae have been killed. Ora test (Contact acne") The active compounds, the concentration of the active compounds, the times of evaluation and the results can be seen from the following Table 2:

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Bean plants (Vicia faba) which have been'heavily infested with the bean aphid (Doralis fabae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage. 100% means that all the aphids are killed; means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3:

Table 3 (Doralis test) Active compound Active com- Degree of pound C0ndestruccentration tion in 9': in 7: by afterl weight day 0 l 0.1 100 c N 0.01 100 Si 0.001 50 CH; O Z

OC H (known) (C) OCH;,

9 0.1 100 N 0.01 100 I H 0.001 95 0.0001 40 -P(oc11u12 (4) O-C H -i O 0.1 100 I 0.01 100 N 0.001 99 fi 0.0001 70 0 2 )2 (6) 0 0 1 100 l 0 01 100 I N 0001 95 i O 1 (o(:1-1,) (1) I 0 l 100 N 0 01 100 s 0 001 99 2H5 O P z s Table 3-Continued (Doralis test) Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent which contains the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris) which have a height of approximately 10 30 cm are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with the twospotted spider mite (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of the active compound is determined by counting the dead mites. The degree of destruction thus obtained is quoted as a percentage: means that all of the spider mites have been killed and 0% means that none of the spider mites have been killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 4:

Table 4 (Tetranychus test/ resistant) Table-4-Continued 7 Table 5 ('Tetranychus'test/resistant) v1 (Mosquito lar ae test) Active compound Active com- De f Active compound Active com- Degree of pound condestruc- 5 pound condcstruccentration tion in 7: centralion t On in in by after 2 of the solu- 71 weight days PP 9 N 10 0 10 100 CI I s 0.1 0 I 1 100 c I N 0.1 100 O--P(OCH 0.01 0

nown) (A) o -P 0C.H.). OCH] (kno n) (B) O l N s 0.1 90 0 v 100 H t 2.. 2:; O (3) HOCZHS) CI I i 0C H i P(OCH;,).,

O (known) (A) N S 0.1 95 I 10 00 0 H N 1 100 (7) 3) Cl 0.1 100 o J}! c H 0.01 90 oc.H.-i 0C H 0 (known) (C) I 3 N 0.1 90 s 0.01 y 40 0 10 100 o --P(OC2 s)2 N l (6) l I E 0:01 30 o (ocz slz P (known) (E) 40 N 0.1 99 Isi 0.01 80 O P 0c.,l-|,)2 1 Q l 10 100 C l 1 100 (H 100 EXAMPLE 5 u 0.01 100 0 (oc m) 0.001 30 Mosquito larvae test (known) (F) Test insects: Aedes aegyptr larvae Solvent: 99 parts by weight of acetone Emulsifier: l-part by weight of benzylhydro ydiphenyl CH polyglycol ether I To produce a suitable preparation of active compound, 2 parts by weight of the active compound are lo 100 dissolved in 1,000 parts by volume of the solvent con- N l 100 taining the amount of emulsifier stated above. The so- 0 E C2": 0 lution thus obtained is diluted with water to the desired lower concentrations. OCZH The aqueous preparations of the active compounds (known) (D) are placed in glass vessels and about 25 mosquito lar- 0 Cl vae are then placed in each glass vessel. 1 100 After 24 hours, the degree of destruction is deteri w v O 1 I00 mined as a percentage. 100% means thatrall the larvae I (H 100 are killed. 0% means that no larvae at all are killed. v 88 The active compounds, the concentrations of the aco 0:000] tive compounds, the test animals and the results can be z r)z seen from the following Table 5: (2)

Table -Continued (Mosquito larvae test) Active compound Active com- Degree of pound condestruccentration tion in of the solu- 7( tion in ppm O-C;,H i

100 1 100 O 0.1 100 l 0.01 100 I N 0.001 100 lSI 0.0001 80 O 2 s)2 OC H -i l 10 100 O 1 100 l 0.1 100 N 0.01 100 i 0.001 80 O P 0CH0.

a 10 100 l 100 N 0.1 100 S 0.01 100 H 0.001 90 O P(OCH3)2 10 100 9 1 100 0.1 100 N 0.01 100 S 0.001 100 1] 0.0001 100 O -P(OC H 0.00001 80 EXAMPLE 6 LT test for Diptera Test insects: Aedes aegypti Solvent: Acetone 2 parts by weight of active compound are dissolved test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed. The time which is necessary for a knockdown effectis determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% knock-down effect can be seen from the following Table 6:

Table 6 (LT test for Dipteru) Active compound Active com- LT pound concentrution of the solution in /z o --P(0Cz 5)2 (known) (B) Q l c l N 0.2 120' S 0.02 l8()' 0 ll (known) S o OC2H5)2 (known) (E) 0 I C l N 0.2 120' 0.02 180' o 2 5)2 (known) (F) O l 0.2 60' N 0.02 o E/ (known) cl 0.2 60' 0.02 60' 0.002 120' I O 1 (oc,1i.-,

Table 6-Continued Table 7-Continued Active compound mo EXAMPLE 7 LT test for Diptera Test insects: Musca domestica Solvent: Acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per cm of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed. The time which is necessary for a 100% knockdown effect is determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% known-down effect can be seen from the following Table 7:

(known) (l) (LT test for Diptera) Active compound Active com- LT pound con centrution of the solution in 71 O P 0C2 5 (2) 0 0.2 45' l 0.02 N 0.002 210' s il cm.

OC H EXAMPLE 8 LD test Test insects: Sitophilus granarius Solvent: Acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per cm of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed. The time which is necessary for a knockdown effect is determined.

The test insects the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% knock-down effect can be seen from the following Table 8:

Table 8 (LD test/Sitophilus granarius) Table 8-Continued (LD test/Sitophilus granurius) Active compound Actve com- Des- Active compound Actve com- Despound contruction pound contruction centrations in 71 centrations in '72 of the soluof the solution in 7: tion in 7:

CH3 0.2 100 0'0 Q02 90 000 100 Br 0.0002 60 D N 9 Cl 1 N l s o P(OC H5)2 l 5 I (known) (F) (8) o u):

O t l 0.2 100 CI i 0.02 100 0.002 V 0 0 P(ocnu cl (known) (A) O 0.2 100 0.02 100 I 0.002 90 Cl 0 il 0.2 100 5 OCH; 0 0.02 100 I 0.002 100 I N 0.0002 0 S I EXAMPLE 9 (2) (QC-1 5).

Test with parasitic fly larvae Solvent: parts by weight of ethylene glycol monomethyl ether 35 35 parts by weight of nonylphenol polyglycol ether cl To produce an appropriate preparation of the active 0.2 100 o 0.02 100 compound, 30 parts by weight of the active substance IN 0002 100 in question are mixed with the stated amount of solvent 00002 90 which contains the above-mentioned amount of emulsifi fier, and the concentrate thus obtained is diluted with (I) OP(OCH3 2 water to the desired concentration.

Q2 m0 About 20 fly larvae (Lucilia cuprina) are introduced OCHa 0.02 100 into a test tube which contains a cottonwool plug which I 51885 8 is impregnated with nutrient medium. 0.5 ml of the ac- Q tive-compound preparation is placed on this medium. I After 24 hours the degree of destruction in percent is determined. Here, 100% means that all larvae have been killed and 0% means that no larvae have been 0 4mm killed. (4) The active compounds investigated, the concentra- OCH 83 :88 tions tested and the findings obtained can be seen from 0.002 100 the following Table 9: I 00002 O T bl 9 a e 9 I N (Test with parasitic fly larvae) fl Active compound Active com- Degree of o z 5)2 pound condestruccentration lion in "/1 in ppm (Lucilia cuprina) (3) 0.2 100 100 I00 0 0.02 100 CI 30 100 0.002 [00 10 I00 I N 0.0002 0 O 3 mo 5 i 1 O o -P(ocH.-.)2 S

Table 9-Continued (Test with parasitic fly larvae) Active compound Active com- Degree of pound condestruccentration tionin 92 in ppm (Lucilia cuprina) l OC HJ O 100 100 N 30 100 T i0 100 Q -P(0C.H. 3 l 0 OC H i I00 100 30 100 10 100 N S 3 0 H o -P(OCH 0 I00 100 30 100 N 10 100 I i 3 100 l 0 o z 5 )2 100 100 P 30 100 N 10 0 l s 3 0 0 -P 0 :H. z

The process of the present invention is illustrated in and by the following preparative Examples.

EXAMPLE 10 I (n o -P 0CH.).

A mixture of 66 g (0.33 mole) of 3-hydroxy-7- chlorobenzisoxazole (melting point: 210C) in 350 ml of acetonitrile and 58 g (0.42 mole) of potassium car bonate is stirred for 30 minutes at 40 to 50C and is subsequently treated, at 25C, with 56 g (0.75 mole) of 0,0-dimethylthionophosphoric acid ester chloride. Thereafter, the reaction mixture is stirred for a further 24 hours at room temperature. The salt-like precipitate which has separated out is then filtered off. The solvent is largely distilled from the filtrate under reduced pressure. The residue is treated with water and the oil which has separated out is taken up in benzene. The benzene solution is washed with 2 N sodium hydroxide solution. After drying the organic layer, the benzene is distilled off. The oil which remains crystallizes after a short time. Colorless, fine crystals of 0,0-dimethyl-0- [7-chloro-ben2isoxazol( 3 )yll-thionophosphoric acid ester of melting point 84C are obtained in a yield of 73 g (70.5% of theory).

The following compounds can be prepared analogously:

Formula Physical properties 0 -P 0C2H.). (2)

ocn

O l I i n 1.5309

II o -2 s)2 OCH;,

9 NS melting point 64C 0 P C 3)Z I N i n,,: 1.5512

C H Z 5 O- P OC H OC H;i

3 N i n,,: 1.5212 OP( z s)z OC;,H,i

O I z N s O P(OCH)2 n [.5311

Continued It will be appreciated that the instant specification Formula Physical properties and examples are set forth by way of illustration and not limitation, and that various modifications and Br changes may be made without departing from the spirit and scope of the present invention.

What is claimed is: 1. The compound 0,0-dimethyl-0-[7-chlorobenzisoxaz0l(3)yl]thionophosphoric acid ester of the formula Other compounds which may be similarly prepared include:

O-butyl 0-[ 7-isobutoxy-benzisoxazol( 3 )yl]- propanephosphonic acid ester, O-isopropyl-0-[ 7-flu0 ro-benzisoxazol( 3 )yl ]-hexanephosphonic acid ester, and the like.

O P(OCH:})2

70 2. The compound 0,0-diethyl-O-[7-chlorobenzisoxazol(3)yl]thionophosphoric acid ester of the formula melting point 82C CI l (2) I N i O- 2 s)2 3. The compound 0-ethyl-0-[7-chloro- 21 I 15735 benzisoxazol(3)yl1-ethanethionophosphonic acid ester of the formula O l N i C H 2 5 melting point 63C 40 2 5 4. The compound 0,0-diethyl-0-[7-iodo benzisoxaz0l(3)yl]-thionophosphoric acid ester of the formula 

1. THE COMPOUND 0,0-DIMETHYL-0-(7-CHLORO-BENZISOXAZOL(3)YL)TIONOPHOSPHORIC ACID ESTER OF THE FORMULA
 2. The compound 0,0-diethyl-0-(7-chloro-benzisoxazol(3)yl)thionophosphoric acid ester of the formula
 3. The compound 0-ethyl-0-(7-chloro-benzisoxazol(3)yl)-ethanethionophosphonic acid ester of the formula
 4. The compound 0,0-diethyl-0-(7-iodo-benzisoxazol(3)yl)-thionophosphoric acid ester of the formula 